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| United States Patent |
5,147,463
|
|
Eilerman
, et al.
|
September 15, 1992
|
Cyclic acetals
Abstract
This invention provides novel cyclic acetals useful as delayed release
flavorants and odorants having the general formula:
##STR1##
These compounds possess no detectable flavor or odor themselves at normal
temperatures and atmospheric conditions but release an aldehyde flavorant
upon heating at higher temperatures. The novel cyclic acetals of the
present invention may be used as flavorants in tobacco compositions or
tobacco substitutes, as sustained flavorants and odorants to mask or
enhance the flavors and odors of burning tobacco products, as flavor
additives to microwaveable foods, and in the preparation of chewing gums.
| Inventors:
|
Eilerman; Robert G. (Merrick, NY);
Christenson; Philip A. (Midland Park, NJ);
Yurecko, Jr.; John M. (Dayton, NJ);
Mild; Frank (Westwood, NJ);
Kucharski; Peter E. (Yardley, PA)
|
| Assignee:
|
BASF K&F Corporation (Whippany, NJ)
|
| Appl. No.:
|
395628 |
| Filed:
|
August 18, 1989 |
| Current U.S. Class: |
131/277; 549/365 |
| Intern'l Class: |
A24B 003/12; C07D 031/02 |
| Field of Search: |
131/276,277
549/365
|
References Cited
| Foreign Patent Documents |
| 109281 | Nov., 1987 | JP.
| |
| 211391 | Dec., 1988 | JP.
| |
Other References
Wood, Harry B. et al., "1,2,:4,6-Di O-benzylidene .alpha.-D-glucopyranose
and Improvements in the Preparation of 4,6-O-Benzylidene-D-glucopyranose"
J. Am. Chem. Soc. 79:1986 (1957).
Joniak, D. et al., "Preparation of some methyl-D-glucopyranoside cyclic
acetals by transacetylation":, Chem. zesti 31(1) 106-108 (1977).
Jedlinski, Z. et al., "The Synthesis, Structure and Properties of Some
Unsaturated Methyl-D-Hexapyranoside Acetals: Univ. Adama. Miekiewicza
Pozhaniu, Wydz. Mzt., Fiz." Chem. [Pr], Ser. Chem. 18.
|
Primary Examiner: Million; V.
Attorney, Agent or Firm: Kenyon & Kenyon
Claims
What is claimed is:
1. A compound represented by the formula:
##STR29##
where R.sup.1 is H or C.sub.1 to C.sub.6 alkyl; R is Ar or Ar.sup.1,
with Ar equal to 3-ethoxy-4-hydroxyphenyl or 5-methylthiophen-2-yl, and
Ar.sup.1 is
##STR30##
with A representing phenyl, 4-methoxyphenyl or 3-methoxy-4-hydroxyphenyl,
such that when A is phenyl, R.sup.2 is C.sub.1 to C.sub.6 alkyl;
when A is 4-methoxyphenyl, R.sup.2 is H or C.sub.1 to C.sub.6 alkyl; and
when A is 3-methoxy-4-hydroxyphenyl, R.sup.2 is H.
2. A compound as defined in claim 1 where R represents Ar.
3. A compound as described in claim 1 where R represents Ar.sup.1, A
represents phenyl and R.sup.2 is C.sub.1 to C.sub.6 alkyl.
4. A compound as defined in claim 1 where R represents Ar.sup.1, Ar.sup.1
represents
##STR31##
A represents 4-methoxyphenyl and R.sup.2 is H.
5. A compound as defined in claim 1 where R represents Ar.sup.1,
Ar.sup.1 is
##STR32##
A represents 3-methoxy-4-hydroxyphenyl and R.sup.2 is H.
6. A compound as defined in claim 1 having the name:
methyl 4,6-0-(4-hydroxy-3-ethoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxyphenyl)prop-2-enylidene glucopyranoside;
methyl 4,6-0-(5-methylthiophenemethylide) glucopyranoside;
methyl 4,6-0-[3-(4-methoxyphenyl)prop-2-enylidene]glucopyranoside; and
methyl 4,6-0-(3-phenyl-2-pentylprop-2-enylidene) glucopyranoside or
methyl 4,6-0-(3-phenyl-2-hexylprop-2-enylidene) glucopyranoside.
7. A smoking composition which comprises natural tobacco or a tobacco
substitute in combination with an organoleptically effective amount of a
compound represented by the formula Ib:
##STR33##
where R.sup.1b represents H or C.sub.1 to C.sub.6 alkyl;
R.sup.b is Ar.sup.b or Ar.sup.1b, with
Ar.sup.b equal to 3-ethoxy-4-hydroxyphenyl,
3-methoxy-4-hydroxyphenyl, 4-methoxyphenyl,
3,4-methylenedioxyphenyl or heteroaryl, and Ar.sup.1b is
##STR34##
with A.sup.b equal to phenyl, 4-methoxyphenyl, 3-methoxy-4-hydroxphenyl,
3,4-methylenedioxyphenyl, or heteroaryl, and
R.sup.2b is H or C.sub.1 to C.sub.6 alkyl.
8. A smoking composition as described in claim 7 wherein the compound has
the name:
methyl 4,6-0-(4-hydroxy-3-ethoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxyphenyl)prop-2-enylidene glucopyranoside;
methyl 4,6-0-(5-methylthiophenemethylide) glucopyranoside;
methyl 4,6-0-[3-(4-methoxyphenyl)prop-2-enylidene]glucopyranoside;
methyl 4,6-0-(3-phenyl-2-pentylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-phenyl-2-hexylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxybenzylidene) glucopyranoside;
methyl 4,6-0-(4-methoxybenzylidene)glucopyranoside;
methyl 4,6-0-(3-phenylprop-2-enylidene)glucopyranoside;
methyl 4,6-0-(3-furanylprop-2-enylidene)glucopyranoside;
methyl 4,6-0-(3,4-methylenedioxybenzylidene) glucopyranoside, or
methyl 4,6-0-(3-(3,4-methylenedioxyphenyl)prop-2-enylidene)glucopyranoside.
9. A smoking composition according to claim 8 wherein the concentration of
said compound is between about 5 ppm and about 50,000 ppm by weight of the
tobacco or tobacco substitute.
10. A media suitable for enclosing tobacco or a tobacco substitute, which
contains between about 5 ppm and about 50,000 ppm of a compound having the
name:
methyl 4,6-0-(4-hydroxy-3-ethoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxyphenyl)prop-2-enylidene glucopyranoside;
methyl 4,6-0-(5-methylthiophenemethylide) glucopyranoside;
methyl 4,6-0-[3-(4-methoxyphenyl)prop-2-enylidene]glucopyranoside;
methyl 4,6-0-(3-phenyl-2-pentylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-phenyl-2-hexylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxybenzylidene) glucopyranoside;
methyl 4,6-0-(4-methoxybenzylidene)glucopyranoside;
methyl 4,6-0-(3-phenylprop-2-enylidene)glucopyranoside;
methyl 4,6-0-(3-furanylprop-2-enylidene)glucopyranoside;
methyl 4,6-0-(3,4-methylenedioxybenzylidene) glucopyranoside, or
methyl 4,6-0-(3-(3,4-methylenedioxyphenyl)prop-2-enylidene)glucopyranoside.
11. A food product comprising a foodstuff in combination with an amount of
a compound represented by formula Ia:
##STR35##
where R.sup.1a represents H or C.sub.1 to C.sub.6 alkyl;
R.sup.a is Ar.sup.a or Ar.sup.1a, with
Ar.sup.a representing 3-ethoxy-4-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl,
4-methoxyphenyl or heteroaryl,
and Ar.sup.1a represents
##STR36##
with A.sup.a representing phenyl, 4-methoxyphenyl,
3-methoxy-4-hydroxyphenyl or heteroaryl, and R.sup.2a representing H or
C.sub.1 to C.sub.6 alkyl.
12. A food product according to claim 11 wherein the compound is present in
a amount ranging from about 0.05% to about 5.00% by weight.
13. A food product as described in claim 11 comprising a baked foodstuff in
combination with a compound as described therein in an amount effective
for imparting flavor to said foodstuff upon baking.
14. A baked food product according to claim 13 wherein the amount of said
compound present in the foodstuff product ranges from about 0.05% to about
5.00% by weight.
15. A food product as described in claim 11 further comprising a
microwavable foodstuff in combination with a compound as described therein
in an amount effective for imparting flavor to said foodstuff upon
microwave cooking.
16. A microwavable food product according to claim 15 wherein the
concentration of said compound is between about 0.05% and 5.00% by weight.
17. A microwave food product according to claim 15 wherein said foodstuff
is a cake, cookie, cracker, bread, or toasted cereal.
18. A chewing gum base composition comprising a gum base in combination
with a compound represented by formula Ia:
##STR37##
where R.sup.1a represents H or C.sub.1 to C.sub.6 alkyl;
R.sup.a is Ar.sup.a or Ar.sup.1a, with
Ar.sup.a representing 3-ethoxy-4-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl,
4-methoxyphenyl or heteroaryl,
and Ar.sup.1a represents
##STR38##
with A.sup.a representing phenyl, 4-methoxyphenyl,
3-methoxy-4-hydroxyphenyl or heteroaryl, and R.sup.2a representing H or
C.sub.1 to C.sub.6 alkyl.
said compound being present in an amount effective for imparting flavor to
said gum base upon mastication thereof.
19. A chewing gum base according to claim 18 wherein the amount of said
compound present in said gum base ranges from about 0.1% to about 10.0% by
weight.
20. A method of flavoring a food comprising treating a food with an
organoleptically effective amount of a compound of the formula I:
##STR39##
where R.sup.1 is H or C.sub.1 to C.sub.6 alkyl; R is Ar or Ar.sup.1 ,
with Ar equal to 3-ethoxy-4-hydroxyphenyl or 5-methylthiophen-2-yl, and
Ar.sup.1 is
##STR40##
wherein A represents phenyl, 4-methoxyphenyl or 3-methoxy-4-hydroxyphenyl,
such that when A is phenyl, R.sup.2 is C.sub.1 to C.sub.6 alkyl;
when A is 4-methoxyphenyl, R.sup.2 is H or C.sub.1 to C.sub.6 alkyl, and
when A is 3-methoxy-4-hydroxyphenyl, R.sup.2 is H.
21. The method of claim 20 wherein the food is a microwavable food.
22. A method of flavoring a chewing gum base comprising adding to the
chewing gum base an organoleptically effective amount of a compound of
formula I:
##STR41##
wherein R.sup.1 is H or C.sub.1 to C.sub.6 alkyl; R is Ar or Ar.sup.1,
with Ar equal to 3-ethoxy-4-hydroxyphenyl or 5-methylthiophen-2-yl, and
Ar.sup.1 is
##STR42##
with A representing phenyl, 4-methoxyphenyl or 3-methoxy-4-hydroxyphenyl,
such that when A is phenyl, R.sup.2 is C.sub.1 to C.sub.6 alkyl:
when A is 4-methoxyphenyl, R.sup.2 is H or C.sub.1 to C.sub.6 alkyl, and
when A is 3-methoxy-4-hydroxyphenyl, R.sup.2 is H.
23. A method of flavoring tobacco comprising adding to the tobacco an
organoleptically effective amount of a compound of formula I:
##STR43##
wherein R.sup.1 is H or C.sub.1 to C.sub.6 alkyl; R is Ar or Ar.sup.1,
with Ar equal to 3-ethoxy-4-hydroxyphenyl or 5-methylthiophen-2-yl, and
Ar.sup.1 is
##STR44##
with A representing phenyl, 4-methoxyphenyl or 3-methoxy-4-hydroxyphenyl,
such that when A is phenyl, R.sup.2 is C.sub.1 to C.sub.6 alkyl;
when A is 4-methoxyphenyl, R.sup.2 is H or C.sub.1 to C.sub.6 alkyl, and
when A is 3-methoxy-4-hydroxyphenyl, R.sup.2 is H.
24. A method of flavoring a smoking composition comprising treating tobacco
or a tobacco substitute with an organoleptically effective compound having
the name:
methyl 4,6-0-(4-hydroxy-3-ethoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxyphenyl)prop-2-enylidene glucopyranoside;
methyl 4,6-0-(5-methylthiophenemethylide) glucopyranoside;
methyl 4,6-0-[3-(4-methoxyphenyl)prop-2-enylidene] glucopyranoside;
methyl 4,6-0-(3-phenyl-2-pentylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-phenyl-2-hexylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxybenzylidene) glucopyranoside;
methyl 4,6-0-(4-methoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-phenylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-furanylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3,4-methylenedioxybenzylidene) glucopyranoside, or
methyl 4,6-0-(3-(3,4-methylenedioxyphenyl)prop-2-enylidene)glucopyranoside.
25. A method of flavoring a smoking composition which comprises natural
tobacco or a tobacco substitute comprising treating the tobacco or tobacco
substitute with an organoleptically effective amount of a compound
represented by the formula Ib:
##STR45##
where R.sup.1b represents H or C.sub.1 to C.sub.6 alkyl; R.sup.b is
Ar.sup.b or Ar.sup.1b, with
Ar.sup.b equal to 3-ethoxy-4-hydroxyphenyl,
3-methoxy-4-hydroxyphenyl, 4-methoxyphenyl,
3,4-methylenedioxyphenyl or heteroaryl, and Ar.sup.1b is
##STR46##
with A.sup.b equal to phenyl, 4-methoxyphenyl, 3-methoxy-4-hydroxyphenyl,
3,4-methylenedioxyphenyl, or heteroaryl, and
R.sup.2b is H or C.sub.1 to C.sub.6 alkyl.
26. A method according to claim 25 wherein the concentration of said
compound is between about 5 ppm and about 50,000 ppm by weight of the
tobacco or tobacco substitute.
27. A method of flavoring a medium suitable for enclosing tobacco or a
tobacco substitute, comprising treating said medium with between about 5
ppm and about 50,000 ppm of a compound having the name:
methyl 4,6-0-(4-hydroxy-3-ethoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxyphenyl)prop-2-enylidene glucopyranoside;
methyl 4,6-0-(5-methylthiophenemethylide) glucopyranoside;
methyl 4,6-0-[3-(4-methoxyphenyl)prop-2-enylidene] glucopyranoside;
methyl 4,6-0-(3-phenyl-2-pentylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-phenyl-2-hexylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-methoxy-4-hydroxybenzylidene) glucopyranoside;
methyl 4,6-0-(4-methoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-phenylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-furanylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3,4-methylenedioxybenzylidene) glucopyranoside, or
methyl 4,6-0-(3-(3,4-methylenedioxyphenyl)prop-2-enylidene)glucopyranoside.
28. A method of flavoring a food product comprising treating a foodstuff
with an organoleptically effective amount of a compound represented by
formula Ia:
##STR47##
where R.sup.1a represents H or C.sub.1 to C.sub.6 alkyl; R.sup.a is
Ar.sup.a or Ar.sup.1a, with
Ar.sup.a representing 3-ethoxy-4-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl,
4-methoxyphenyl or heteroaryl,
and Ar.sup.1a represents
##STR48##
with A.sup.a representing phenyl, 4-methoxyphenyl,
3-methoxy-4-hydroxyphenyl or heteroaryl, and R.sup.2a representing H or
C.sub.1 to C.sub.6 alkyl.
29. A method according to claim 28 wherein the compound is present in an
amount ranging from about 0.05% to about 5.00% by weight.
30. A method as described in claim 28 further comprising baking the
foodstuff in combination with a compound as described therein in an amount
effective for imparting flavor to said foodstuff upon baking.
31. A method of flavoring a chewing gum base composition comprising
treating a gum base with an organoleptically effective amount of a
compound represented by formula Ia:
##STR49##
where R.sup.1a represents H or C.sub.1 to C.sub.6 alkyl; R.sup.a is
Ar.sup.a or Ar.sup.1a, with
Ar.sup.a representing 3-ethoxy-4-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl,
4-methoxyphenyl or heteroaryl,
and Ar.sup.1a represents
##STR50##
with A.sup.a representing phenyl, 4-methoxyphenyl,
3-methoxy-4-hydroxyphenyl or heteroaryl, and R.sup.2a representing H or
C.sub.1 to C.sub.6 alkyl.
said compound being present in an amount effective for imparting flavor to
said gum base upon mastication thereof.
32. A method according to claim 30 wherein the amount of said compound
present in said gum base ranges from about 0.1% to about 10.0% by weight.
Description
FIELD OF THE INVENTION
This invention relates to novel cyclic acetals useful as delayed release
flavorants and odorants. The invention also provides a process for the
synthesis of these compounds as well as smoking and flavorant compositions
which incorporate the invention. The compounds of the invention are used
as sustained release odorants which are incorporated in the media
enclosing the tobacco. They may also be used as flavor additives to
microwaveable foods.
BACKGROUND OF THE INVENTION
Flavor additives have long been used to flavor a wide variety of consumer
products, particularly tobacco products, foodstuffs, and gums. Flavor
additives in such products may be used to mask or attenuate undesirable
flavors or odorants, and to enhance existing flavors or odors, or to
provide additional flavors or odors not initially present in the consumer
product.
A principal strategy currently employed to impart flavors or odors to
consumer products is the admixing of the flavorant chemicals within a
matrix that slows or prevents their release until the product is
pyrolyzed, heated, masticated or wetted. Alternatively, the flavoring
chemical may be covalently bound to an auxilliary component to form a
higher weight molecule of low volatility. The flavorant is then released
upon pyrolysis, heating or solvolysis of the tobacco or food product.
For example, European patent 186,502 describes the use of a plastic capsule
that releases flavorants when mechanically crushed.
U.S. Pat. No. 4,001,438 describes flavor compositions for use in orally
utilizable compositions which may be either chewing gum compositions,
chewable medicinal tablets, chewing tobacco or toothpaste. The flavor is
controllably released from the flavor compositions over an extended period
of time under hydrolytic conditions.
U.S. Pat. No. 4,253,473 describes smoking tobacco compositions or
substitute smoking tobacco compositions which upon smoking release
substantially evenly and uniformly over an extended period of time.
U.S. Pat. No. 3,818,107 describes a chewing gum containing a flavor release
composition comprising polymer backbones with flavor groups appended
thereto. The flavor moieties are released from the polymer backbone by
hydrolysis which is achievable by mastication of chewing gums containing
the flavor groups.
As an alternative method, the flavoring chemicals may be covalently bound
to an auxilliary component to form a higher molecular weight molecule of
low volatility. The flavorant is released upon pyrolysis, heating or
solvolysis of the tobacco or food product.
In general, inventions employing the second strategy use an ester or
carbonate linkage of a higher molecular weight molecule to an alcoholic
flavor molecule. In such a system a flavor molecule is covalently bound to
a polymer and may be depicted by the following generalized structure:
##STR2##
wherein R.sub.1 represents a low alkyl group such as methyl, R.sub.2
represents a flavorant radical such as menthyl and n is an integer from 2
to 10,000. This approach has been demonstrated in a number of U.S.
Patents. For example, U.S. Pat. No. 4,212,310 describes different flavored
smoking tobacco products wherein some of the products contain an alcohol
flavorant-release composition which delivers the flavor note of the
alcohol upon pyrolysis.
U.S. Pat. No. 4,119,106 describes alcohol flavorant-release polymeric
derivatives which are designed to enhance tobacco smoke by releasing an
alcohol flavorant to tobacco smoke without wasting the natural flavor of
the resultant main stream tobacco smoke.
U.S. Pat. Nos. 4,578,486 and 4,538,628 describe smoking tobacco
compositions which contain dioxane diester flavorant-release additives.
When subjected to normal smoking conditions such as cigarettes, the
diester additive decomposes to release a volatile pyrolysis (alcohol or
phenol) component which provides flavor-enhancing properties to the
mainstream smoke and enhances the aroma of the sidestream smoke.
U.S. Pat. Nos. 4,701,282, 4,538,627 and 4,540,004 describe the use of
ketoester or carbonate ester compounds as flavorant additives which under
cigarette smoking conditions pyrolyze to release flavorants which enhance
the flavor of the mainstream smoke and the aroma of sidestream smoke.
Acetals have also been used as vehicles to covalently bind aldehyde
flavorants. For example, U.S. Pat. No. 4,296,137 describes the use of
1-ethoxy-1-ethanol acetate or a flavor or fragrance enhancer of a wide
variety of consumable materials. The 1-ethoxy-1-ethanol acetate compound
has the ability to liberate acetaldehyde in smoking tobacco. U.S. Pat. No.
4,280,011 describes the use of acetals as aldehyde generators in foodstuff
applications. U.S. Pat. No. 3,625,709 describes food flavoring and aroma
enhancers consisting of acetaldehyde combined with carbohydrates to form
compositions which release acetaldehyde when combined with hot water or
with cold water. U.S. Pat. No. 4,857,964 describes controlled release
flavor compositions useful in flavor compositions which comprise flavor
particles formed from a dispersion of flavor acetal or ketal in polymeric
binders. The controlled release flavor compositions have multiple means of
control, one of which is the hydrolysis of the flavor acetal or ketal.
These controlled release flavor compositions are useful in chewing gums.
Finally, U.S. Pat. Nos. 4,690,157 and 4,607,118 describe tobacco
compositions which contain flavor release additives which, under cigarette
smoking conditions, pyrolyze in a "retro-aldol" fragmentation reaction
into products which enhance the flavor and aroma of the cigarette smoke.
It is one object of the present invention to provide a series of novel
compounds, as well as methods for their synthesis, useful as flavorants
and as sustained release odorants to mask and/or to enhance the odors of
burning tobacco products.
Another object of the present invention is to flavor cooked foods, e.g.,
microwaveable foods, which, during the cooking process, release flavorants
into the food.
Yet another object of the present invention is to flavor chewing gum.
SUMMARY OF THE INVENTION
In accordance with the above-mentioned objects and other objects, the
following invention is directed to the class of novel cyclic acetal
compounds having the formula:
##STR3##
where R.sup.1 is H or C.sub.1 to C.sub.6 alkyl;
R is Ar or Ar.sup.1, with Ar equal to 3-ethoxy-4-hydroxyphenyl or
5-methylthiophen-2-yl, and Ar.sup.1 equal to
##STR4##
with A representing phenyl, 4-methoxyphenyl or 3-methoxy-4-hydroxyphenyl,
such that when A is phenyl, R.sup.2 is C.sub.1 to C.sub.6 alkyl; when A is
4-methoxyphenyl, R.sup.2 is H or C.sub.1 to C.sub.6 alkyl, and when A is
3-methoxy-4-hydroxyphenyl, R.sup.2 is H.
The invention described herein further encompasses a method of flavoring a
food comprising adding to a foodstuff an effective amount of a compound of
formula Ia:
##STR5##
where R.sup.1a is H or C.sub.1 to C.sub.6 alkyl;
R.sup.a is Ar.sup.a or Ar.sup.1a, where Ar.sup.a represents
3-ethoxy-4-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl, 4-methoxyphenyl or
heteroaryl, and Ar.sup.1a is
##STR6##
with A.sup.a representing phenyl, 4-methoxyphenyl,
3-methoxy-4-hydroxyphenyl or heteroaryl, and R.sup.2a represents H or
C.sub.1 to C.sub.6 alkyl.
The invention described herein further encompasses a method of flavoring
tobacco or tobacco paper comprising adding to said tobacco or tobacco
paper an effective amount of a compound of formula Ib:
##STR7##
where R.sup.1b is H or C.sub.1 to C.sub.6 alkyl;
R.sup.b is Ar.sup.b or Ar.sup.1b, with Ar.sup.b equal to
3-ethoxy-4-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl, 4-methoxyphenyl,
3,4-methylenedioxyphenyl or heteroaryl, and Ar.sup.1b is
##STR8##
with A.sup.b representing phenyl, 4-methoxyphenyl,
3-methoxy-4-hydroxyphenyl, 3,4-methylenedioxyphenyl or heteroaryl and
R.sup.2b is H or C.sub.1 to C.sub.6 alkyl.
DETAILED DESCRIPTION
As used herein the term "organoleptic" refers to compounds of the invention
which stimulate the sense of smell or taste, and are thus perceived as
having a characteristic odor and/or flavor.
The terms "odor", "fragrance" and "smell" are used interchangeably whenever
a compound is referred to as an organoleptic which is intended to
stimulate the sense of smell.
The terms "flavor", "flavoring" and "flavorant" are also used
interchangeably whenever and organoleptic compound is referred to which in
intended to stimulate the sense of taste.
An "organoleptically effective amount" is a level or amount of a novel
cyclic acetal compound(s) present in a material at which the incorporated
compound(s) exhibit(s) a sensory effect.
The terms "tobacco" and "tobacco substitutes" are used in the conventional
sense and include smokable as well as non-smokable forms in which tobacco
is regularly used, e.g., cigarettes, snuff, chewable compositions, etc.
The term "tobacco paper" refers to smokable paper used to contain tobacco,
e.g., tobacco rolling paper.
The following chemical terms are used throughout the specification, and are
defined as follows unless otherwise indicated:
Acetal--an organic compound formed by addition of an alcohol to an
aldehyde.
Alkyl (including the alkyl portion of alkoxy, alkylthio aralkyl and
heteroaralkyl)--branched or unbranched saturated carbon chain containing 1
to 20 carbon atoms, with lower alkyl representing a chain containing 1 to
6 carbon atoms.
Heteroaryl--aromatic group having 5 to 6 atoms in a ring, 1 to 3 of which
are heteroatoms contained in the aromatic ring, selected from O, S or N,
with the remaining atoms being carbon atoms, the group being sufficiently
unsaturated to provide aromatic character to the ring.
Preferred compounds falling within the scope of the invention include those
compounds where Ar, Ar.sup.a and Ar.sup.b are 3-ethoxy-4-hydroxyphenyl,
and where A, A.sup.a and A.sup.b are phenyl.
The preferred value of R.sup.1, R.sup.1a and R.sup.1b is H.
Compounds falling within the scope of formula I which are preferred
include:
methyl 4,6-0-(4-hydroxy-3-ethoxybenzylidene) glucopyranoside;
methyl
4,6-0-[3-(3-methoxy-4-hydroxyphenyl)prop-2-enylidene]glucopyranoside;
methyl 4,6-0-(5-methylthiophene-2-methylide) glucopyranoside;
methyl 4,6-0-[3-(4-methoxyphenyl)prop-2-enylidene]glucopyranoside;
methyl 4,6-0-(3-phenyl-2-pentylprop-2-enylidene) glucopyranoside, and
methyl 4,6-0-(3-phenyl-2-hexylprop-2-enylidene) glucopyranoside.
Preferred compounds for use in flavoring foods and beverages include those
compounds recited above which fall within the scope of formula I, plus the
following compounds falling within the scope of formula Ia:
methyl 4,6-0-(3-methoxy-4-hydroxybenzylidene) glucopyranoside;
methyl 4,6-0-(4-methoxybenzylidene) glucopyranoside;
methyl 4,6-0-(3-phenylprop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-(4-methoxyphenyl)prop-2-enylidene) glucopyranoside;
methyl 4,6-0-(3-(3-methoxy-4-hydroxyphenyl)
prop-2-enylidene)glucopyranoside; and
methyl 4,6-0-(3-furanylprop-2-enylidene)glucopyranoside.
Preferred compounds useful for flavoring tobacco or tobacco paper include,
in addition to the compounds recited above falling within the scope of
formulae I and Ia, the following compounds falling within the scope of
formula Ib:
methyl 4,6-0-(3,4-methylenedioxybenzylidene) glucopyranoside, and
methyl 4,6-0-(3-(3,4-methylenedioxyphenyl)prop-2-enylidene)glucopyranoside.
The compounds described herein may exist in several isomeric forms. The
present invention includes both essentially pure isomeric forms as well as
mixtures thereof.
The novel cyclic acetals of the present invention may be used as flavorants
in tobacco compositions, as sustained release odorants to mask or enhance
the odors of burning tobacco products, as flavor additives for
microwaveable foods, and in the preparation of chewing gums.
Under normal temperature and atmospheric conditions the cyclic acetals
exist as stable solids which have no detectable odor. Upon heating to
higher temperatures or upon chewing, as in the case of a chewing gum, the
flavorant is released.
The novel cyclic acetal compounds of the present invention are
substantially odorless and tasteless under normal temperatures and
atmospheric conditions, e.g., about 10.degree.-50.degree. C. and about 20
to 100% relative humidity, and exist as stable solids. However, when
heated to higher temperatures, e.g., about 70.degree. C. to about
300.degree. C., in the presence of moisture or steam, they undergo a
transformation in which the odor or flavor is released. This
transformation may be represented by the following Scheme I.
##STR9##
The aromatic aldehyde obtained from the transformation of Scheme I is
useful as a flavorant or odorant.
Illustrative structures of species which can be made in accordance with the
teachings herein are shown below in Table I.
TABLE I
__________________________________________________________________________
##STR10## methyl 4,6-0-(4-hydroxy-3- ethoxybenzylidene
) glucopyranoside
##STR11## methyl 4,6-0-(3,4-methylene- dioxybenzyliden
e) glucopyranoside
##STR12## methyl 4,6-0-(4-methoxy- benzylidene)
glucopyranoside
##STR13## methyl 4-6-0-(4-hydroxy-3- methoxybenzyliden
e) glucopyranoside
##STR14## methyl 4,6-0-(5- methylthiophenemethylide)
glucopyranoside
##STR15## methyl 4,6-0-(3- phenylprop-2-enylidene)
glucopyranoside.
##STR16## methyl 4,6-0-[3-(4- methoxyphenyl)prop-2-
enylidene] glucopyranoside.
##STR17## methyl 4,6-0-(3-phenyl-2- pentylprop-2-enyli
dene) glucopyranoside
##STR18## methyl 4,6-0-(3-phenyl-2- hexylprop-2-enylid
ene) glucopyranoside
__________________________________________________________________________
The cyclic acetals according to structure Ia may be prepared by the
reaction of the flavorant with a pyranoside as shown in the following
scheme II.
##STR19##
According to Scheme II, a pyranoside XII is reacted with the flavorant
ethyl vanillin XIII in the presence of a suitable solvent, acid catalyst
and dehydrating agent. The preferred solvents are aprotic solvents such as
acetonitrile, dimethyl acetamide, methylene chloride, N-methylpyrrolidone,
1,2-dichloroethane, toluene and xylene. The more preferred solvent is
dimethylformamide. The preferred acid catalysts include sulfuric acid,
nitric acid, trifluoroacetic acid, boron trifluoride, hydrochloric acid,
methanesulfonic acid, zinc chloride, magnesium chloride and magnesium
bromide. The more preferred acid catalyst is p-toluenesulfonic acid. The
more preferred dehydrating agents include triethylorthoformate,
trimethylorthoacetate, magnesium sulfate (anhydrous) and sodium sulfate
(anhydrous). The more preferred dehydrating agent is triethylorthoformate.
A dehydrating process involving the azeotropic removal of water using a
solvent such as toluene may also be used.
Compounds of formulae Ia and Ib are prepared in accordance with the above
teachings, taking into account the examples contained herein.
The cyclic acetal compounds of the invention possess organoleptic
properties and therefore permit the development of methods useful in
enhancing the flavor of foods. These compounds are also useful in
enhancing the odor, masking any unpleasant odor or enhancing the flavor of
tobacco products.
These compounds may be used individually in an amount effective to enhance
a characteristic flavor or odor of a material. More commonly, however, the
compounds are mixed with other flavor or fragrance components in an amount
sufficient to provide the desired flavor or odor characteristic.
The amount required to produce the desired, overall effect varies depending
upon the particular compound chosen, the product in which it will be used,
and the particular effect desired.
For example, depending upon the selection and concentration of the cyclic
acetals used, addition of the cyclic acetals either singly or as a mixture
to cigarette tobacco at levels ranging from about 5 ppm to about 50,000
ppm tends to enhance the smoking flavor and/or mask undesirable smoking
odors. An important property of these cyclic acetals is that the flavorant
or odorant is covalently bound as a non-volatile compound and it is only
when the tobacco product is ignited and burns that the flavorant or
odorant is released.
Addition of the cyclic acetals of formula I either separately or as a
mixture at levels ranging from about 5 ppm to about 50,000 ppm by weight
onto the media enclosing the tobacco serves to incorporate the
odorant/flavorant in the side-stream smoke as the tobacco product burns.
Air borne flavorants and/or odorants along with other combustion products
are thus introduced. This newly formed odorant or flavorant serves to
enhance or mask the smoking odors depending upon selection and use levels
of the cyclic acetals.
The cyclic acetals of the present invention are particularly useful in the
flavoring and aromatizing of cooked foods. Addition of the cyclic acetals
either singly or as a mixture to a cake batter, e.g., a microwave cake
batter, serves to impart appropriate baking aromas to the cake as it is
heated in the microwave as well as impart flavoring in the finished
product. Typically, the cyclic acetals are employed at levels ranging from
about 0.05 to about 5.00%.
The flavor of chewing gum may also be enhanced by the addition of cyclic
acetals of formula I. A selected cyclic acetal or mixture of cyclic
acetals is kneaded into a gum base at levels ranging from about 0.1% to
about 10.0% by weight. The appropriate flavors are released in the
resulting gum upon mastication.
The compounds of the invention may be incorporated in the foodstuff or
tobacco product along with other ingredients. Such other ingredients
include emulsifiers, carriers, binders, sweeteners, stabilizers, buffers
and solvents.
The following examples are given to illustrate embodiments of the invention
as it is preferred to practice it. It will be understood that these
examples are illustrative and the invention is not to be considered to be
restricted thereto.
All parts, proportions, percentages, and ratios used herein are by weight
unless otherwise indicated.
EXAMPLE 1
Methyl 4,6-0-(4-Hydroxy-3-Ethoxybenzylide) Glucopyranoside
##STR20##
Ethyl vanillin (21.5 g, 0.13 mol), methyl glucopyranoside (25.0 g, 0.13
mol), acetonitrile (100 mL), trimethylorthoformate (15.4 g, 0.15 mol) and
p-toluenesulfonic acid (0.2 g) were combined in a 500 mL round bottom
flask and heated for 18 hours at reflux. Ethyl acetate (500 mL) was added
to the warm solution which was washed with brine, then saturated sodium
bicarbonate solution. The mixture was dried (Na.sub.2 SO.sub.4),
concentrated to a final volume of 200 mL and allowed to stand at 0.degree.
C. The resulting crystals were collected and dried to yield the product.
mp 178.degree.-180.degree. C., [.alpha.].sup.D.sub.20 =+72.80.H.sup.1 -NMR
(CD.sub.3 OD) .delta.7.06 (1H,J=1.8 Hz), 26.93 (dd, 1H, J=8.4, 1.8 Hz),
6.77 d, 1H, J=8 Hz), 5.47 (s,1H), 4.7 (d, 1H, J=4.0 Hz), 4.28-4.00 (m,
3H), 3.87-3.62 (m, 3H), 3.54-3.46 (m, 1H), 3.42 (s, 3H), 3.34-3.26 (m,
2H), 1.40 (t, 3H, J=7.0 Hz). .sup.13 C NMR (CD.sub.3 OD) .delta.148.6,
17.7, 130.8, 120.7, 115.8, 112.8, 103.2, 102.0, 82.8, 74.1, 72.1, 70.0,
65.8, 63.9, 55.8, 15.1, IR (KBr), 3530, 3420, 3310, 2925, 2860, 1660,
1512, 1437, 1415, 1370, 870 cm.sup.-1, MS m/e (% abundance) 343 (8), 342
(38), 167 (68), 166 (100), 138 (60), 109 (28), 87 (20), 45 (75).
EXAMPLE 2
Methyl 4,6-0-(3-Phenylprop-2-Enylidene)Glucopyranoside
##STR21##
A mixture of cinnamic aldehyde (3.2 kg, 24.2 mol), methyl glucopyranoside
(4.7 kg. 24.2 mol), dimethyl formamide (16L), trimethylorthoformate (2.8
kg, 26.6 mol) and p-toluenesulfonic acid monohydrate (80 g) was heated at
95.degree. C. for 4 h. The mixture was neutralized with 40% sodium
hydroxide solution. Most of the solvents were removed under reduced
pressure. The residue was taken-up in ethyl acetate (12L) and the
resulting solution was washed with brine. Concentration of the solution
and crystallization provided the product. mp 147.degree.-149.degree. C.,
[.alpha.].sub.D 104.degree.. .sup.1 H-NMR (CD.sub.3 OD) .delta.7.5-7.2
(m,5h), 6.84(d,1H, J=16.7 Hz), 6.20 (dd,1H, J=16.7 Hz and 4.0 Hz), 5.20
(d, 1H, J=4.7 Hz), 4.72 (d, 1H, J=4.0 Hz), 4.10-4.25 (m, 1H), 3.87-3.0
(m,5H), 3.43 (s, 3H). .sup.13 C-NMR (CD3OD) .delta.137.5, 134.9, 129.6,
129.2, 127.7, 125.9, 102.2, 102.0, 82.5, 74.2, 72.1, 69.7, 63.9, 55.8, IR
(KBr) 3300, 1660, 1595, 1575, 1480, 1450 cm.sup.-1. MS m/e (% abundance)
309 (2), 308 (12), 144 (12), 131 (40), 104 (100), 74 (22, 45 (70).
EXAMPLE 3
Methyl 4,6-0-(4-Methoxybenzylidene) Glucopyranoside
##STR22##
In a fashion similar to the procedure described in Example 2, anisic
aldehyde and methyl glucopyranoside are combined to form methyl
4,6-O-(4-methoxybenzylidene) glucopyranoside. mp 209.degree.-210.degree.
C., [.alpha.].sub.D= +63.28.degree.. .sup.1 H-NMR (CD.sub.3 OD) 7.48 (d,
2H, J=8.8 Hz), 6.89 (d, 2H, J=8.8 Hz), 5.51 (s, 1H), 4.72 (d, 1H, J=3.7
Hz). .sup.13 C NMR (CD.sub.3 OD) .delta.131.5, 128.8, 114.4, 103.0, 102.0,
101.4, 82.9, 75.0, 72.1, 71.6, 70.0, 63.9, 55.8. IR (KBr) 3350, 2930,
1445, 1360, 1240, 805, 607 cm.sup.-1. Ms m/e (abundance) 312(19), 137
(100), 136 (50), 135 (80), 133 (50)<74 (32), 45 (50).
EXAMPLE 4
Methyl 4,6-0-(4-Hydroxy-3-Methoxybenzylidene) Glucopypranoside
##STR23##
In a fashion similar to the procedure described in Example 2, vanillin and
methyl glucopyranoside are combined to form methyl 4,6-O
-(4-hydroxy-3-methoxybenzylidene) glucopyranoside. mp
207.degree.-208.5.degree. C., [.alpha.9 .sub.D =+74.5.degree.. .sup.1
H-NMR (CD.sub.3 OD) .delta.7.08 (d, 1H, J=1.3 Hz), 6.93 (dd, 1H J=8.4, 1.8
Hz), 6.7 .delta.(d, 1H, J=8.4 Hz), 5.48 (5, 1H, 4.72 (d, 1H J=3.7 Hz),
4.26-4.12 (m, 1H), 3.84 (s, 3H), 3.83-3.58 (m, 3H), 3.55-3.37 (m, 1H),
3.42 (s, 3H), .sup.13 C NMR (CD.sub.3 OD) .delta.148.6, 148.3, 130.9,
120.6, 115.7, 103.2, 102.0, 82.9, 74.2, 72.1, 70.0, 63.9, 56.7, 55.8, IR
(KBr) 3580, 3510, 3310, 3100, 2950, 2900, 1620, 1525, 1460, 1435
cm.sup.-1. MS m/e (relative abundance) 324 (4), 328 (28), 327 (7), 311
(2), 297 (2), 225 (4), 219 (2), 152 (86), 133 (30), 45 (100).
EXAMPLE 5
4,6-0-(3,4-Methylenedioxybenzylidene) Glucose
##STR24##
In a fashion similar to the procedure described in Example 2, piperonal and
glucose combined to form 4,6-O-(3,4-methylenedioxybenzylidene) glucose. mp
172.degree.-173.degree. C. [.alpha.].sub.D =+11.4, .sup.1 H-NMR (CD.sub.3
COCD.sub.3) .delta.7.01-6.94 (m, 2H), 6.84-6.79 (m, 1H), 6.00 (s, 2H),
5.49 (s, 1H), 5.17 (d, 1H, J=3.6 Hz), 3.2-4.7 (m, 5H), 2.89 (broad s, 3H).
IR(KBr) 3580, 2900, 1680, 1605, 1500 1445 cm.sup.-1. MS m/e(rel.
abundance) 314(I), 313(2), 312(14), 311(2), 294(2), 223(10), 149(100),
121(25), 93(30), 43(40).
EXAMPLE 6
Methyl 4,6-O-(5-Methylthiophenemethylide) Glucopyranoside
##STR25##
In a fashion similar to the procedure described in Example 2,
5-methylthiophenecarboxaldehyde and methyl glucopyranoside were reacted to
form methyl 4,6-0-(5-methylthiophenemethylidene) glucopyranoside. mp
167.degree.-168.degree. C., [.alpha.].sub.D =+69.9.degree., .sup.1 H-NMR
(CD.sub.3 OD) .delta.6.93 (d, 1H=3.5 Hz), 6.64 (d, 1H, J=3.5 Hz), 5.74 (s,
1H), 4.72 (d, 1H, J=3.6 Hz), 4.10-4.25, (m, 1H) 3.30-3.85 (m, 5H), 3.43
(s, 3H), 2.46 (s, 3H), .sup.13 C-NMR (CD.sub.3 OD) .delta.126.75, 125.39,
102.05, 99.99, 87.12, 82.84, 74.15, 71.98, 69.97, 63.74, 55.83, 15.07, IR
(KBr) 3330, 2900, 2840, 1440, 1360 cm.sup.-1. MS m/e (% abundance) 305
(0.5), 304 (1), 303(4), 302(20), 271(2), 199 (8), 127 (100), 74 (60),
45(50).
EXAMPLE 7
Methyl 4,6-0-[3-(4-Methoxyphenyl)Prop-2-Enylidene]Glucopyranoside
##STR26##
Methyl glucopyranoside and p-methoxycinnamic aldehyde were reacted in a
fashion similar to that described in Example 2 to provide the product. mp
148.degree.-150.degree. C. [.alpha.].sub.D 70.0.degree. (c, 1.13,
methanol). .sup.1 H-NMR (CD.sub.3 OD) .delta.7.36 (d, 2H, J=8.9 Hz), 6.89
(d, 2H, J=8.9 Hz), 6.76 (d, 1H, J=15.7 Hz), 6.07 (dd, 2H, J=15.7 and 4.6
HZ), 5.17 (d, 1H, J=4.6 Hz), 4.7 (d, 1H, J=3.7 Hz), 4.21-4.08 (m, 1H0,
3.80 (s, 3H), 3.85-3.2 (m, 5H), 3.41 (s, 3H). .sup.13 C-NMR (CD.sub.3 OD)
.delta.161.3, 134.5, 130.2, 129.0, 123.6, 115.1, 102.6, 102.0, 82.5, 74.2,
72.0, 69.7, 63.9, 55.8, IR (KBr), 3450, 1680, 1610, 1530, 1060, cm.sup.-1.
MS m/e 338, 307, 247, 179, 161, 121 (134,100%).
EXAMPLE 8
Methyl 4,6-0-(3-Phenyl -2-Pentylprop-2-Enylidene) Glucopyranoside
##STR27##
Methyl glucopyranoside and .alpha.-pentyl cinnamic aldehyde were reacted
in a fashion similar to that described in Example 2 to provide the
product. mp 146.degree.-147.degree. C. [.alpha.].sub.D 63.5.degree. (c,
1.36, methanol). .sup.1 H-NMR (CDCl.sub.3) .delta.7.4-7.2 (m, 5H), 6.73
(s, 1H), 5.02 (s, 1H), 4.79 (d, 1H, J=4.5 Hz), 4.25 (dd, 1H, J=6.7 and
4.0), 4.0-3.35 (m, 5H), 2.95 (d, 1H, J=3.4 Hz), 2.50 (d, 1H, J=8.9 Hz),
2.34 (t, 2H, J=7.8 Hz), 1.62-1.24 (m, 6H), 0.89 (t, 3H, J=6.7 Hz). .sup.13
C-NMR (CDCl.sub.3) .delta.138.3, 137.0, 129.2, 128.8, 126.8, 104.2, 100.0,
81.0, 73.2, 72.0, 68.9, 62.6, 55.5, 32.1, 28.6, 27.8, 22.3, 13.9. IR (KBr)
3420, 1540, 1055, 860, 740 cm.sup.-1. MS m/e 378, 307, 287, 275 (131,
100%).
EXAMPLE 9
Methyl 4,6-0-(3-Phenyl-2-Hexylprop-2-Enylidene)Glucopyranoside
##STR28##
Methyl glucopyranoside and .alpha.-hexyl cinnamic aldehyde were reacted in
a fashion similar to that described in Example 7 to provide the product,
mp 148.degree.-148.5.degree. C., [.delta.]d 72.1.degree. (c, 1.66
methanol). .sup.1 H-NMR (CDCl.sub.3) .delta.7.36-7.15 (m, 5H), 6.72 (s,
1H), 5.06 (s, 1H), 4.71 (d, 1H, J=4 HZ), 4.19-4.13 (m, 1H), 3.83-3.15 (m,
5H), 3.43 (s, 3H), 2.36-2.28 (m, 2H), 1.65-1.1 (m, 8H), 0.87 (t, 3H, J=6.5
Hz), .sup.13 C-NMR (CD.sub.3 OD) .delta.140.0, 138.4, 130.1, 129.7, 129.2,
127.9, 105.4, 102.0, 82.7, 74.2, 72.1, 69.8, 64.0, 55.8, 32.5, 30.6, 29.8,
28.5, 23.5, 14.3, IR (KBr) 3430, 1600, 1065, 965, 750, 690 cm.sup.-1. MS
m/e 392, 363, 331, 307, 275, 241, (31, 100%).
EXAMPLE 10
Preparation of a Microwave Cake Mix Base
A microwave cake mix base was prepared by mixing the following ingredients:
______________________________________
A. Ingredient Parts
______________________________________
Sugar 398.0
Shortening 50.0
Emulsifying Agents
2.0
Cake Flour 392.8
Corn Syrup Solids 50.0
Dextrose 50.0
Leavening Agents 28.2
Salt 8.5
Cornstarch 5.0
Xanthan Gum 5.0
Sodium Caseinate 1.0
Flow Aid 8.5
1000.0
______________________________________
From this cake mix a batter was prepared using the following formula:
______________________________________
B. Ingredient Parts
______________________________________
Microwave Cake Mix 46.46
(from Part A)
Water 30.60
Scrambled Egg 9.56
Corn Oil 13.38
100.00
______________________________________
0.1 g of the product of Example 1 was added to 99.9 g of the cake batter.
The batter was then processed in a 650 watt microwave oven for 5 minutes.
The resulting cake was determined to possess a sweet, vanilla odor and
taste.
EXAMPLE 11
Preparation of Sweet Vanilla Microwave Cake Mix Base
0.1 g of the product of Example 4 was added to 99.9 g of the cake batter of
Example 6. The resulting cake was determined to possess a sweet, vanilla
odor and taste.
EXAMPLE 12
Preparation of Anisaldehyde Microwave Cake Mix Base
0.1 g of the product of Example 3 was added to 99.9 g of the cake batter of
Example 6. The resulting cake possessed anisaldehyde odors and flavors.
EXAMPLE 13
Preparation of a Chewing Gum
0.1 g of the product of Example 3 was added to 99.9 g of chewing gum base.
The resulting chewing gum possessed sweet notes due to anisaldehyde.
EXAMPLE 14
Preparation of Vanillin Cigarette
A 1% solution of the product of Example 1 in ethanol was applied to
cigarette papers to produce levels of 5-50,000 ppm of the flavorant. The
paper was incorporated in cigarettes and, upon burning, released a strong
vanillin odor.
EXAMPLE 15
Preparation of a Cinnamaldehyde Cigarette
A 1% solution of the product of Example 2 in ethanol was applied to
cigarette papers to produce levels of 5 to 50,000 ppm of the flavorant.
The paper was incorporated in cigarettes and upon burning, released a
strong cinnamaldehyde odor.
EXAMPLE 16
Preparation of a .alpha.-Hexylcinnamaldehyde Cigarette
A 1% solution of the produce of Example 9 in ethanol was applied to
cigarette papers to produce levels of 5 to 50,000 ppm of the flavorant.
The paper was incorporated in cigarettes and upon burning, released a
strong floral jasmine-like odor with a herbal note.
EXAMPLE 17
Preparation of a Cigarette Containing a Vanillin Flavored Tobacco
A 1% solution of the product of Example 1 in ethanol was injected onto the
tobacco of a typical American Blend Cigarette at a level of 100 ppm. Prior
to smoking, no odor of vanillin was observed. Upon smoking, the mainstream
and sidestream smoke displayed a strong vanillin odor.
EXAMPLE 18
Preparation of Cigarette Containing .alpha.-Hexylcinnamaldehyde Flavored
Tobacco
A 1% solution of the product of Example 9 in ethanol was injected onto the
tobacco of a typical American Blend cigarette at a level of 100 ppm. Prior
to smoking, no odor due to .alpha.-hexylcinnamaldehyde was observed. Upon
smoking the mainstream and sidestream smoke was less harsh than an
unflavored cigarette and displayed a strong floral jasmine-like odor along
with a clean fresh note.
While certain preferred embodiments have been described herein in detail,
numerous alternative embodiments are contemplated as falling within the
spirit of the invention. Consequently, the scope of the appended claims is
not to be limited thereby.
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